Process for breaking petroleum emulsions employing certain oxyalkylated pentaerythritols



July 12, 1960 M. DE GROOTE EI'AL 44, 7

PROCESS FOR BREAKING PETROLEUM EMULSIONS EMPLOYING CERTAIN OXYALKYLATED PENTAERYTHRITOLS Filed May 24. 1954 Ca Ho PENTAERYTHRITOL IOO IN V EN TOR-5' A B car-46 0 4 a W 2,944,919 rRocEss FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING CERTAIN OXYALKYLATED PENTAERYTHRITOLS Melvin De Groote, University City, and Owen H. Pet- Kirkwood, Mo.,- assignors toPetrolite Corporation, Wilmington, Del., a corporation of Delaware FiledMay 24,1954, Ser. No. 431,788 20 Claims. Cl. 252-331 V This invention relates to processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleuni emulsions. Y

7 52,944,979 Patented July 12, 1960 ICC The oxyalkylation of a liquid or a solid which can be melted at comparatively low temperature (under 150 C.) without decomposition or is soluble in aninert solvent, such as xylene, presents little or no mechanical difficultiesin the oxyalkylation step. When one has a solid which cannot be melted, or decomposes on melting, and is insoluble in xylene a slurry may be employed as in the case of the oxyalkylation of sucrose. See US. Patent No. 2,652,394, dated September 15, 1953, to De Groote.

Our invention provides an economical and rapid process tor. 'resolv'ing'petroleum emulsions of the water-in-oil type that are commonly referredft'o as cut oil, roilly oil, erirulsifiedoilfl etc., and which comprisefiiie' drop lets of naturally-occurring waters or'brines dispersed in a more or les'spe'rmanent state throughout the'oil which constitutes-the continuous phase of the emulsion. It also provides an economical and rapid process for separating emulsions which have been preparedunder controlled conditions "from. mineral oil, such as. crude oil and relatively soft waters or-weak brides Controlled emulsification and subsequentfldemulsification under the conditions just mentioned are ,of significant valuelin' removing impurities particularly inorganic salts,- from pipelineoil. V I

More specifically then the-present invention is concerned with a process for breaking petroleum emulsions employinga demulsifier including a cogeneric mixture of a homologous series of glycol ethers of pentaerythritol. The cogeneric mixtures are derived exclusively from pentaerythritol, ethylene oxide, propylene oxide and butylene oxide, in such weight proportions so the .averagecomposition of said cogeneric mixture in termsvof'the initial reactants lies approximately within the truncated triangular pyramid identified as E, H, 'F, I and G, J, in Figure 1; with the proviso that the percentage of ethylene oxide, by weight,is within the limits of 2% to 39.5% and. the remaining three initial reactants recalculated to 100% basis lie approximately within the triangular area defined in Figure 2 by points 1, 4, 6. However, as will be pointed out subsequently the same ultimate compositions may be employed using any one .of the three oxides last. The oxyalkylation of. pentaerythritol by means ofethylene oxide, propylene oxide, or butylene oxide has been described in the literature. One can use instead of the oxides the corresponding alkylene carbonates, to wit, ethylene carbonate, propylene carbonate, or butylene carbonate.

Asis well known, the oxyalkylation derivatives from any oxyalkylation-susceptible compound, are prepared by the addition reaction betweensuch oxides andsuch. compound. The addition reaction is advantageously carried out at an elevated temperature and pressure and 'in the presence of a small amount of alkaline catalyst. Usually, the catalyst is sodium hydroxide or sodium methylate. The reaction temperature is apt to be 140 C.'or somewhat less, and the reaction pressure not in excess of 30 to 50 pounds per square inch.

As to further information in regard to the mechanical steps involved in oxyalkylation, see US. Patent No.

Actually, as far 'as oxyalkylating a slurry of a xyleneinsoluble solid in xylene the procedure is substantially the same for pentaerythritol, polypentaerythritol,sorbitol or sucrose. 7

' The oxyalkylation of pentaerythritol can be accomplished in a number of ways and the particular procedure is immaterial. Such procedure has been described in numerous patents and specific reference is made to the instant application which is concerned with ethylene oxide and butylene oxide or the equivalents. Actually, whether one uses ethylene oxide or butylene oxide or, for that matter, propylene oxide one preferably starts with powdered pentaerythritol suspended in a slurry in xylene or a similar unreactive solvent; or one employs an alkylene carbonate such as ethylene carbonate, butylene carbonate or propylene carbonate for the initial oxyalkylation. When such initial oxyalkylation has gone far enough to convert the solid mass into a product which is at least liquid at oxyalkylation temperature it can be subjected to the oxides as differentiated from the carbonates. The carbonates, of course, cost more than the oxides.

When butylene oxide is' used the same procedure can be followed as in the use of propylene oxide or ethyleneoxide as described in US. Patent 2,652,394, dated September 15, 1953, to De Groote. Indeed, the oxyalkylation of pentaerythritol is substantially comparable to the oxyalkylation of sorbitol, particularly it one used powdered sorbitol in the form of a slurry. Such slurry is the 2,499,365, dated March 1, 1950, to De Groote et al. I

Particular reference'is made to columns 92 et'seq'.

equivalent of a slurry of powdered pentaerythritol.

In the use of butylene oxide the same procedure can be employed as in the oxypropylation of tripentaerythritol as described in US. Patents 2,626,907 and 2,626,908, both dated January 27, 1953, and both to De Groote. See also what appears in US. Patent 2,552,528, dated March 15, 1951, to De Groote. See also Examples 8a through 12a, inclusive, in US. Patent 2,626,906, dated January '27, 1953, to De Groote. In essence,we have found we can oxybutylate pentaerythritol in the same manner conventionally employed for oxypropylation, for example, we have found the directions which appear in columns 5, 6, 7 and 8 of aforementioned US. Patent 2,626,908, in regard to oxyethylation or oxypropylation of tripentaerythritol are just as suitable in regard to the oxybutylation of pentaerythritol. We have completed the reactions under the same conditions set forth in Examples.

1a through 4a usingbutylene oxide and varied the procedure only in that the time required was somewhat slightly longer.

Numerous other patents include specific information as to the oxypropylation of pentaerythritol and pentaerythritol polymers. Actually the procedure is substantially the same whether one uses butylene oxide, propylene oxide or ethylene oxide. I It is not believed any examples are necessary to illustrate such well known procedure but for purpose of illus tration the following are included.

Example 1a The reaction vessel employed was a-stainless steel autoclave with the usual devices for heating, heat con trol, stirrer, inlet, outlet, etci, whicn is conventional in 3 this type of apparatus. The capacity was approximately 4 liters. The stirrer operated at a speed of approximately 250 r.p.m. There were charged into the autoclave 500 grams of pentaerythritol, 300 grams of xylene, and 15 grams of sodium methylate; The autoclave was sealed, swept with nitrogen gas and stirring started immediately and heat applied. The temperature was allowed to rise to approximately 145 C. Attliis particular'time'the addition of butylene oxide was started. The butylene oxf ide employed was a mixture of the straight chain isomer substantially free from isobutylene oxide. It was added continuously at such speed that it was absorbed by the reaction as added. The amount added in this operation was 1500 grams. The time required to add the butylene oxide was two hours. During this period the temperature was maintained at 128 C. to 145 C., using cooling water through the] inner coils when necessary and otherwise applying hear if required. The maximum pressure during the reaction was 48 pounds per square inch. Ignoring the xylene and sodium methylate and considering the penta'erythritol for convenience, the resultant product represents 3 parts by weight of butylene oxide to one part by weight of pentaerythritol. The xylene present represented approximately .6 of one part by weight.

Example 2a The reaction mass was transferred to a larger autoclave (capacity 15 liters). Without adding any more solvent or any more xylene the procedure was repeated so as to add another 1500 grams of butylene oxide under substantially the same operating conditions but requiring about .3 hours for the addition. At the. end of this step the ratio represented approximately 6 to 1 (ratio butylene oxide to pentaerythritol).

Example 3a In a third step, instead of adding 1500 grams of butylene oxide, 1625 grams were added. The reaction slowed up and required approximately hours, using the same operating temperatures and pressures. The ratio at the end of the third step was 9.25 parts by weight of butylene oxide per weight of pentaerythritol.

Example 411 At the end of this step the autoclave was opened and an additional 5 grams of sodium methylate added, the autoclave flushed out as before, and the fourth and final oxyalkylation completed, using 1625 grams of butylene oxide, and theoxyalkylation was complete within hours using the same temperature range and pressure as previously. 'At the end of the reaction the product represented approximately 12.5 parts of butylene oxide by weight to one part of pentaerythritol.

All the examples, except the first step, were substantially water-insoluble and xylene-soluble.

As has been pointed out previously these oxybutylated pentaerythritols were subjected to oxyethylation in the same manner described in respect to the oxypropylated pentaerythritol sucrose in aforementioned U.S. Patent No. 2,552,528. Indeed, the procedure is comparatively simple for the reason that one is working with a liquid and also that ethylene oxide is more reactive than butyl ene oxide. As a result, using the same amount of catalyst one can'oxyethylate more rapidly than usually at a lower pressure. There is no substantial diiference as far as operating procedure goes whether one is oxyethylating oxypropylated pentaerythritol or oxybutyl'at'ed pe'ntae'rythritol. 1

The'same procedure using a slurryof finely powdered pentaerythritol in xylene was employed in connection with ethylene oxide and the same mixture on a percentage basis was obtained as in the above examples where butylene oxide and pentaerythritol were used. I s

The same procedures have been employed using other butylene oxides including mixtures having considerable isobutylene oxide and mixtures of the straight chain isomers with greater or lesser amounts of the 2,3 isomer.

Where reference has been made in previous examples to the straight chain isomer; the product used was one which was roughly orinore of the 1,2 isomer and approximately 15% of the 2,3-cisand the 2,3-transisomer with substantially none or not over 1% of the isobutylene oxide.

In the preceding procedures one oxide has been added and then the other. One need not follow this procedure. The two oxides can be mixed together in suitable proportions and subsequently subjected tojoint oxyalkylation so as to obtain products coming. within the specified limits. In such instances, of course, the oxyalkylation may be described as random oxyalkylation insofar that one cannot determine the exact location of the butylene oxide or ethylene oxide groups. In such instances the procedure again is identically the same as previously described and, as a matter of fact, we have used such methods in conhection with molten sorbitol.

If desired, one may add part of one oxide and all of the "other and then returhto the use or the first oxide, for instance; or one may use the procedure as previously, adding first some butylene oxide, then ethylene oxide and then the butylene oxide. Or, inversely; one may add some ethylene oxide, then all butylene oxide and then the remainder of the ethylene oxide; or either oxide could be added in portions so that first one oxide is added, then the other, then thefirst oxide is added again,.and then the second oxide. We have found no advantage in so doing. Indeed, our preference has been to add all the butylene oxide first and then the required amount of ethylene oxide. I

g I As pointed out previously, pent'aery'thritol can be o'xyethylated in the same way it is oxyhutylated, i'.'e., by preparing a slurry in xylene or in a similar solvent and 'using a suitable alkaiin'e' catalyst such as caustic soda, sodium methylate, or the like, and then adding the ethyl ene oxide. The changes previously mentioned are of difference in degree only. In other words, oxyethylation willtake place at 'a lower temperature, for instance, a top temperature -of probably to C. instead of to C. The 'sarnje weight or ethylene oxide could be added in 75% to 85% of the time required for butylene oxide. The pressure during the reaction, instead of being 35 to '45 pounds in the case of butylene oxide, is apt to be 10 to 15 pounds and at times a little higher. Otherwise, there is no difference. Also,fifj desired, the use of ethylene carbonate is a very convenient way of 'ox'y'e th'yla't'i'ng p'en'taery'thritol. In fact, it eanteex ethylateu without the use of pressure. Such procedure, and particularly melting the carbonate I first and adding the powdered 'pentaerythritol slowly permits th n-sanction of a reaction mass which is; a liquid 'or which melts -readily at comparatively low temperatures "to yield -a liqiuid. Such reaction should be @flductdin such a 'way that there is no residual ethyl ene carbonate or for that matter propylene carbonate when the mass is transferred to an autoclave. In fact, propylene carbonate is more satisfactory than ethylene carbonate. 7

;One.can,oxyalky1ate using an acid catalyst or an al.- kaline catalyst or at least in part, without the :use of any catalyst although "such procedure is extremely slow and uneconomical. In "other words, any one of the convent'ionalcatalys'ts used in oxyakytaaoa may be employed. It is our preference, however, to use an alkaline catalyst such "as sodium methylate, caustic soda, or the like.

'Actuall'y, finely powdered peiita'e'rythr'itdl may contain a trace of moisture. ourp'rrreace is "to. prepare 'the slurry with an excess of xylene and distill off one p'art of the xylene so as to remove any trace of water. and then fiushout the mass withnitro'gen. 'Even so, there ene oxide in this ma a few tenths of apercent of moisture remain although at times examination indicates' at the most'it is procedure can'be followed as,. in the use bipr'oPy'liane oxide as described in Example Part 2 of aforementioned U.S. Patent No; 2,552,528.= The molten pentaerythritol is reacted with the butylene oxide and as oxybutylation takes place the reaction mass becomes a ho mogeneous liquid. For instance, referring to Example A, column 16 of aforementioned patent; we have. used identically ,the same procedure starting with anhydrous finely powdered pentaerythritoL- Instead of'using 1600 grams of propylene oxide, there yvasfused 1800 grams of butyleneoxide (mixed straight chainisomers);

. In Example B, instead of using 1100 grams of-the propylene oxide derived intermediate from Example A, precedingpthere was used instead 1191 grams ofhthe butyleneoxide derived intermediate, Example A. =Insteadof using 1327 grams of propylene oxide .there was added 1493 grams ofbutylene oxide.;, 1

in Example C, instead of using 1149 grams of propylene oxide derived intermediate Example B, from the preamylase o i e derivedintermediate B. "Instead of sading "l99 jgi'ams o fl propyleneioxidefin thisjstagefthere I 1 was added instead 2345 grams of butyleneo x-ide.

there was used 831 gramsof the .butylene oxide deriived intermediate. Instead of adding637 grams of propylbutylene oxide.

' L It will be noted at this stage theratio of-butyleneoxide to pentaerythritol was approximately 100-to-1, and the amount. of pentaerythritol represents less'than 3%, by

"Example E was'conducted in the same manner except i that the initial reactant was Example D, preceding, and

butylene, oxide.

In this lastexample, five grams of sodium methylate wereaadded .asta catalyst, toispe'ed up. thejfinalssta'ge of Operating c onditions; such as temperature, time'factor, Ietc., were substantiallyithe same asides'cribed in thecorresponding Examples A',.: B D, 1.0, and .E, in

reaction.

aforementioned U.S. Batent.2,552,528...f-

It will ben'oted.thatinz thisfinal productfiapproxini-ate ly 00amoles of .butylenefoxide werelemployed per mole of pentaerythritol. On. a'percentage basis, the products represented approximately. 1% pentaerythritol and 99% butylene oxide. I L f. Y'

All examples, except the first stage, were substantially water-insoluble and xylene soluble.

It is immaterial in whatorder the oxides are added to pentaerythritol so as to obtain the herein described products.- However; our preference is to add butylene oxide first, then propylene oxide, and thenethylene oxide. There are two advantages in so-doing. The first advantage is that productsobtained as 'far as the. general average goes following this-succession of oxides 'appears'to pressure on the-'auteqlav thanin dxyethylationf Howp torily,

Soifar the'use of butylene oxide is concerned, we

stated previously as far as the oxyalkylaceding example, there was used instead 1 27 1 -gram s of i stage, there'wasadded 717 grams of lilaqueous solvent.

instead oflusing 566 grams,.-there, was usedinstead 628 4. grams of the reactant. .;Instead .offfadding5 63 grams of propylene oxide, there was. added insteadj633 grams of j F r 7 compositional limits of the herein described invention.

prefer to usethe straight chain isomers i on 011-011 on I ont-on -a-on-om or a mixture of the we. o

As noted previously, one can oxyethylate first and then'add either one of the'other two oxides, to wit,'butyl- "ene oxide or propylene oxide. ':"Similarly, one can add either oxide first, that is, 'propyleneoxide or butylene oxide, and then add ethylene oxide, followed by the'addi tion of the other oxide. Also, as is obvious, one need not add all the ethylene oxide alone or all the'butylene oxide alone or all the propylene oxide alone. One could make a mixture of either one of the two,or all three, and use such mixture or mixtures as an oxyalkylating agent. Furthermore, one can add a fraction of any particular oxide and then add the rest at a subsequent stage. "Ihisma-y be applied not only to a single oxide but also to two of the three, or all three, of the oxides employed. I

,j For the purpose of resolving petroleum emulsions of the .water-infoil type, 'weprefer to employ oxyalkylated derivatives, which are obtained 'by-the use ofmono epoxides, in such manner' that the"derivatives'so-obtained have sufficient hydrophile character to meet at least the testjset forth in U.S. Patent No. 2,499,368, dated March 7,..1950, to De Groote and Keiser. In said patent such .test'tfor emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.- i I m Iheabove mentioned --ficati0ntest simply means that the preferred product for .Tdniiilsification is soluble in a solvent having hydrophobe properties. or in an oxygenated Water-insoluble solvent, or .IT mixture containing a fraction of such solvent with the proviso that when such solution in a hydrocarbon solvent jjisfsliaken with water the product may remain in the nonaqueous solvent or, for that matter, it may pass into the In other words, although it is xylene soluble, for example, it may also be water soluble to an j equal or greater degree.

For-purpose of convenience, what is said hereinafter will be divided into four parts:

- "Part 1 is concerned with theroxyalkylation of penta- Qerythri'tol broadly so as to obtain products within the Part 2 is concerned with binary or tertiary products derived fromipen'taerythritol and a single oxide, orpenta- -:efythrit'ol and-two oxides, whichlinay. be looked uponas intermediate products. More convenientlygthe binary compositions may be considered as sub-intermediates arid component product described in Section 1, preceding.

Part3v is concerned essentially with the oxyalkylation of the intermediate described in Part2, preceding) Needless to say, if the intermediate were obtained by the use of butylene oxide and ethylene oxide it would be subjected to oxypropylation; 'if obtained from butylene oxide and propylene oxide it would be subjected to oxyethylation; and if obtained from propylene oxideand ethylene oxide it would be subjected to oxybutylation; Part 4 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds. 7 1

PART o The present invention is concerned 'with a cogeneric mixture which is the end -prdduet of a reaction 6' 7 tions involving 4 reactants. completeiies's' of test, i.e., aeonventional emulsi- .QE! 1W0 15 4 93 8 he upper ba e. h r t p am L reactionand based on a mathematicalaverage, the final product is cha racteriz edlrnostconveniently sin terms .of

the 4 component rea ctants. phase of theihvention is described elsewhere'ingreater'detail.

In representing a mixture or an end product derived .5 'from '2%' to" 39.i5.% ethylene oxide. "Th'proble'mthen from 2 components or3 components, there is no difficulty p'rsent'edis the-determination 'of'the'other three comas far as using the plane surface of an ordinary printed ponentsftywit, butylene oxide,'ipropylene oxide, and sheet. For example, a B-Chmponent system is usually pentaerythritol. I d r I I v represented by a triangle in which the apexesrepresent simplification of the "problem 'of characterizing a 100% of .eac'hco mponent and anymixture' or reaction 10 'fi component system' which entersinto the spiritof the product'in terms of the '3 components-is representedby present nwention isthisz If the amount of one centa point in the triangular areainwhichtheiwmposition ponentis' determinedor'if a "range is set, for example, is indicated by perpendiculars'from such point to the 2% to 3'9 5%of'ethylene'oxide,then thelditference'besides. V 'twcenthis amountjand 100%, i.'e.,-60.5% to 98%,repre- Chemists andgphysicists ordinarily characterize a '4- .15 fsentsthe amounts of percentage s'of the otherthreecorncomponent system by'usinga solid, -i;e., aregular tetraponents combined, these three components recalhedron. In this particular presentation each point or eulated to 100% basescan=be-"d'etermined by useofan apex represents 100% of each of the 4 components, each ordinary triangular graph. d of the 6 edges represents a line or binary mixture. of the Actually, as far-asithe-limiting points in the truncated '2 components-represented by the apexes or points at the pyramid "are 'concerned, which has been*previously reend of the line or edge. Each of the 4 triangles or faces ferred to in"Figure 1, 'it'will henoted-that in the subrepresent a tertiary mixture of the} components represequent text th'ereis a complete table giving'the comsented by the 3 corners or apexes and obvrously signify position of "these "points for each successive range of the eomplete absence of the 4th component indicated by ethylene oxide. 'In'other' words, a-perfectly satisfactory 'the corner or apex opposite the triangular face. v H 2. repetition is availablebymeans of these tables from a I Howevenassoonas one moves to a point within the practical standpoint without necessarily resorting to thc regular tetrahedron one has definitely characterized; and data-of Figure 2.

' v TABLE I 'Points on Pentalirtopyl- ButyliPenta- Pmpyl- .Penta- .Butyl- 39 1 1 15 eryth- "8H8 "ene "erythone eryth- -ene ofArea ritol, nda- .Qxide, 11501, Oxide; l. O i

. Percent Percent Percent Percent' Percent Percent Percent 3.0 68.5 28.5 4.18 95.82 9.52 $90.48 3.0 75. 0 22. 0 3. 96.15 12. 0 88. 0 2.5 -'83.0 14-5 2. 92 97.08 14.7 7 85.3 7.5 17.5 75.0 330.0 70.0 9.1 90.9 14.0 .225 63.5 38.3 61.7 18.05 81.95 24.0 48.5 27.5 33.1 66.9 46.6 53.4 41.5 25.5 33.0 61.8 38.2 55.7 44.3 27. 5 51. 5 21.0 a4. 8 65. 2 66. 6 43. 4 21.5 145.5 "33.0 -i32.0 68.0 39.4 60.6 17. 0 27. o 56.0 38. 5 61. 4 23. 3 76.6

specified :a 4-con-rponentxmixture in which the '4 components Iadd'up to Such a representation of a 4-.cornponent system is described in :detail in US. 'Patent 2,549.,43S1toDe'Groote etal.

The :invention will :be-described by reference to .the accompanying'drawings; which illustrate, in conventional graphical iforrn,' c'ompositions usediinaccordance with the three may 'bedetermined.

Referring .now to Figure 11, "the composition :represented by theiblockavhich is really atruncated triangular .pyr'amid-isdes'ignated by "E,H;'F, I; and G,.J. Bear in mind that the insect the truncated'pyramid, that is E,

F, G, does not'resti'on thebottom ofthe equilateral base triangle. Point D'represents 100% ethylene oxide. The base triangle representsthe'three other components and obviously 0% ethyleneoxide. For purpose of What is said herein, the lower base" of the truncated pyramid Q, is a'ibaseparallel to theyequilateral triangle,"but

#25 91. -e-l :r pressnfin 2%. of thylene oxi Figure 2 shows a triangle-and the three components other "than ethylene oxide. These three components added togetheraredessfthan 100%, to wit, 60.5% to 98%, but forreasons explained are calculated back to 100%. This point is clarified subsequently by examinationofirthe tables. It 'Will'be noted that-Figure 2 shows :a triangle 1, .4' and 6, which represents the bases (top, bottom, or format matter intermediate) of the truncated'pyramid, also the area in composition'which is particularly pertinent to the present invention.

PART 2 .ethylene oxide :asthe final component and this selection 915A, .3, C, as the base lends itselfmost readily to such presentation. Y I

- vious that hardly any directions are required to produce 3,8,7and 9.

column 8. l

to'obtain the selected intermediate oflpoint 1 canbe prepared in any suitable manner ini oi'propylene oxide.

'tem derived from pentaerythritol, propyleneoxide and butylene oxide. Such product, can then be reacted with 2% to 39.5% of ethylene oxidebased on the final com position so as to give the preferred examples of thei'nstant invention.

. Returning now momentarily to the preparation of the S-compOnentintermediate shown in Figure 2, it is ob I the compounds specified. However, referring to the com-. position of the initial reactants based on the triangle in the attached drawing, it will be noted thatwe havecal culated the percentage of the three initial reactants for points 1 to 23, inclusive, so as to yield the intermediate derived from pentaerythritol, propylene oxide, and butylene oxide. These points determine not only the tri angle but also numerous points Within the triangle. Furthermore, the points are selected so the area isdivided into five parts, three of which are trianglesand two of which are four-sided figures. The tr'iangles'are defined by the points 1, 2 and 8; 2, 3 and 8; 5, 6 and 7; and the four-sided figures by' the points 3, 4, 5 and 9 and finally" I Note that these data are included in Table I..sliowniin Note the first column 'gives various QpOint' n'lth boundary of thetrianglei-orwithin thetriangle. Notethe:

next three'columns represent the tertiarvmixturecorre spending to Lthe initial reactants, .i. e.-,: theintermediatei 1 These values: represent percent-ages, weight, ofipentael i' butylene x de and p m ers;ax fle-tigilmsi it is apparent. that onelcan select anyparti-cularpoint in Figure2 andsimply usefthe'appropr' rrrount offoxide; For-instance, in regard to point 1, all thafi'would begmaasswiuquldihe" tomix 86.5 pounds of propylene oxide with-1 2.5-pounds of butylene oxide and use the mixturgtojoxyfllgylateonei; pound of pentaerythritolx Similarly, in Example 2, one need] only mix i63 poui1f ds of propylene oxide with 36 pounds of butylene oxide -and' use the mixture to oxyalkylate CiQQlli und jofjjpenta-; erythritol in a manner previously indicated.- Note that the fifth and sixth columns represent binary mixtures; for instance, in regard to the various points on the'triangle and Withinthe triangle, we have calculated the initial mixture using pentaerythritol and propylene oxide' in the first place and using pentaerythritol and; ethylene 'oxidein the secondplace, whichcould be employed for subsequent oxyalkylation to givethe particular. composition required. Stated another way, we have 'calculated the composition for the sirbl-intermediates ,which, when reacted with the. other oxide, propylene oxide; or; butylene oxide as the case may be, givm the interm i.e., the three-component product. 3 I W p WNote that abinary intermediate for the preparation volving 1.14 pounds of pentaerythritol and 98.76 pounds Referring now to the tertiary mixturetable, it is apparent that. for point 1 pentaerythritol and propylene oxide together represent 87.5 and butylene oxide 12.5%. Therefore, one could-employ 87.5 pounds of the binary mixture (a sub-intermediate) and react it with 12 /2 pounds of butylene oxide to give the three-component product (the intermediate).

Similarly, in regard to the fifth and sixth columns-the mixture involved pentaerythritol and propylene oxide. One could employ 1.56 pounds of pentaerythritol and 98.44 pounds of propylene, oxide. Suchmixture need onlybe reacted with butylene oxide in the proportion of: 64 pounds of such mixture and 36-pounds of butylene oxide to giv e the desired l3;componen t;product, ,T-his 'is; obvious from the gdata' in regard to thetertiary mixtures.

Referring now to columns 7 and 8,it is obvious one through and including 23c:

ediate could produce an oxybutylated pentaerythritol and thefi subject it toreaction with propyleneoxide. .Using this procedure in regard to point 1, it is obvious the mixture is obtained by 7.42 pounds of pentaerythn'tol'and 92.58 poundsof butylene oxide. This product can then be subjected to reaction with propylene oxide in the ratio of 13.5pou'nd's of the mixture and 86.5 pounds of'propylene oxide. Similarly, in regard to point 2, it is obvious thaton'e can react 2.70 pounds of pentaerythritol with 97.3 pounds of butylene oxide. 37 p'ounds of this mixture can then be reacted with 63 pounds of propylene oxide.

" As previous ly pointed out, the oxyalkylation of pentaerythritol has been described in the literature and is described also in detail above. All one need do is employ such conventional oxyalkylation procedure to obtain products corresponding to the compositions as de-' ation,'we have prepared exam-j ples three different ways corresponding to the compositions of the so called intermediate in Figure 2. In the first series, butylene oxide and ethylene oxide were mixed;

this series is indicated as 1a, 2a, 3a, through and includ-.

l b, 2b, 3b, through and including 23b. Finally, in the third series propylene oxide was used first, followed by" butylene-oxide and the series identified as 1 2 3 ;TABLE II M v Composition Composition 1 Composition where Butylwhere Propyl- Composition Corresponding where Oxides H ene Oxide ene Oxide to following Point are Mixed a used first used first Prior to Oxyfollowed by followed by alkylation Propylene Butylene Oxide Oxide 1a a. 1b 10 2a 2b 21: 3a 3b a 3e 40. 4b "4c 5a 5b 6a 6b 7a 7b 8a 8b 9a 9b 9:: 10a 10b 10c 11a 11b 7116 12a 12b V 13a 13b 13c 14a 14b 14a 15a 15b 15c 16a 16b 16a 17a 17b 18a 18b 19a 19b 19a 20a 20b 20:: 21a 21b 210 22a' 22b 22a 23a 23b 23c PART 3 I In Part 2 preceding there has been described the preparation of sub-intermediates and intermediates. As previously-noted, these intermediates need only be subjected toconventional oxyethylation to produce the products described in the present invention.,The amount ofethylene oxide employed is suchthat the final composition conforms, to the, composition, set forth in Figure. This means thatthe amount of ethylene oxide usedv 7 as are'actant represents 2% to 39.5% of the final prod- 11? not. with, the proviso. that. the, remainder of, the product is, represented by the three remaining components within thejpropo'rtioiis. set forth in Figure 2. Inpreparingexamples We have.

done nothing more 12 ethyleneoxide. Example F-6cis obtained by reacting 75% ofintermediate, 60 with 25% of ethylene oxide. It Willb'e notedthait' the last series of 7' examples in TablefIV'are concerned with compositions correspond-1 except use conventional oxyethylation, using an'alkaline 5. ing to. pointsjl, 10,.15, 16, 20 and 23 in Figure 2. catalyst. suchas p'owdered'caustic soda or sodium meth- In these. instances the compound having the Fdesignaylate. Wehaveoperated at temperatures varying from tion has 25 ethylene oxide; the one with a G desig- 110" C. to 135 C. We have usedloxyethylation,presnation has 27' /2%; the one with the H designation,'30%; suresof 1O pounds per square, inch up to 3.0" pounds the one with the I designation, 32 /z%; the one'with persquare inch, but usually notover 15"p'ounds persquare 10. the J designation, 35%; the one with the K designation, inch. The time period has varied from 15' minutes when 37 /2 and the one with the L designation, 39 /2 Note just a small amount ofoxide'was employed, up to as that in one instance the table shows all three typesof much as 4 to 6 hours when a larger amount of oxide'was preparation, that is in the, instance of J 16a, 116b, and used. I 16c. The remaining examples in Table IV, following,

Obviously the simplest of calculations is involved; al- 15 are self-explanatory. though we have given the data in tabular form for the TABLE IV reason that we have indicated that the product containmg 2% ethylene oxlde cafrnes h s i .A;' Composition Composition Composition the one having 5% ethylene oxide 63.11185 the. designation 0 c m C d wlere Ox- Where Butywhere Prop I 2 ompos on orrespon i es are lene Oxide iene Oxide B F one having ethyleile' oxide C the ing toiollowing Point Mixed Prior used first; usedfirst" having is D; the one having 15 Brand the toOxyalkylfollowed by followed by one having is F. Similarly, designations G, H, I, a i-fig 625? I, K, and L are products containing 275%" to 39.5% oi'ethylene' oxide, respectively, as shown in Table III; d 16 2a 13-2!) 20 TABLE III ie 0-30 [Proportions by weight] 5: 13-51] Ga. 6b F-6c A-7a 7b 7c S-Compo- 8a 3-81) 80 Ethylene nent Inter- 9a 9b 0-90 Ex.No. Oxide mediate of, Designation. 106 Part 2, 11a E-llb 11c Preceding 1 12a 12b F-l 2c at B as a ll C 2 1A 15a 15!) 0-15: 3 .97 D-lfia 16b 160 4 96 m E-17b 17a 5 95 B 18a 18b F-18c 6 94 A-19a 19b 19c 7 20a 13-200 200 8 92 21a 21!) 0-211: 9 91 0 13-2211. 22b 22c 90 23.1 Iii-23b 23c 11 89 1a 1b F-lc 12 88 G-5a 5b 5c 13 87 10a 11-101; 10c 14 86 D 15a 15b I-15c 1s 85 J'16a J-l6b J-16c is g; 20a K-20b 20c 13 23a 23b L-23c 20 so a g; The same procedures have been employed using other 23 butylene oxides including mixtures having considerable 24 isobutylene oxide andmixtures of the straight chain 25 75 F. 215 G, isomers with greater or lesser amount of the 2,3 isomer. gg-g g Where reference has been made in previous examples 35:0 65 J. to the straightchain isomer, the product used was one which was roughly 85% or more of the 1,2 isomer and approximately 15 of the 2,3-cisand the 2,3 -trans isomer Since it would be impossible to prepare all the vari-v ants which have been previously suggested, Wehave proceeded as follows: We have prepared 30 examples corresponding to the 23 points in: Figure 2 by varying: the amount of ethylene oxide from 2% to 39.5%. One example we have used 2%, another 5%, another 10%, another 15 another 20% and another*25%, and on up to 39.5%, as shown. The intermediates used are thosedescribed in Table II, preceding. The-prepared products have been described as follows: A-la, B-2b, C-3c, D-4a, etc. A-la is, of course, the'product'obtained by using 98% of intermediate la previously described in Table II, and 2%, by weight, of ethylene oxide; Example B-Zb is obviously obtained by reacting 95%, by Weight, of intermediate 25 with 5%,by-weight, oi ethylene oxide. Example C-3c is-obtained="by reacting 90%, by Weight, ofintermediate 3c'with 10%, by weight, of ethylene oxide. Example D4a-is obtainedbyreacting-85 of intermediate 4a with 15 hy'weight, ofi ethylene oxide. Example B-Sbis obtained =byf reacting: 80% of I intermediate-5b with 20%, "by weight, of

with substantially none or not over 1% of the isobutylene. oxide.

In the preceding procedures one oxide has been added and then the other. One need not follow this procedure. The three oxides can be mixed together in suitable proportions and subsequently subjected to joint oxyalkylation so as to obtain products coming within the specified limits. In such instances, of course, the oxyalkylation may be described as random oxyalkyiation insofar that one cannot determine the exact location of the butylene oxide, propylene oxide or ethylene voxide groups. Inv such instances the procedure again is identically the same as previously described, and, asa matter of fact, We

have used such methods in connection with pentaerythritol.

If desired, one may add part of one oxide and'then all the others and then return to the use of the first oxide. For example, one might use the procedure previously suggested, adding some butylene oxide, all the propylene oxide, all theethylene'oxide and then the remainder of the-butylene oxide. Or, inversely, one may add some propylene oxide, then all the butylene oxide, then the of ethylene oxide.

or less.

'made to glycol ethers of pentaerythritol.

it well may be that the products should be referred to as smears remainder of the propylene oxide, and then the ethylene oxide. Or, any one of the three oxides could be added in portions so one oxide is added first, then other two, then the first oxide is added again, then the other two.

We have found no advantage in so doing;.indeed, our

preference has been to add all the butylene oxide .firs't, then all the propylene oxide, and then the requiredamount As previously pointed out, p'entaerythritol can be oxyparticularly an alkaline catalyst, and adding the ethylene oxide. The changes previously mentioned are of dif ference in degree only. In other words, ,oxyethylation will take place'at a lower temperature, for instance, a top temperature of probably 110 to-135" C. instead of 145 to 150 C. The same weight of ethylene oxide could be added in 75% to 85% of the time required for butylene oxide. of being 2() to 35 pounds as in the case of butylene oxide, is apt to be to 30 pounds and at times a little higher, but frequently operates at pounds'per square inch Otherwise, there is no difference. Note, how- The pressure during the reaction,'instead ever, that it is easier and preferable to oxyethylate last,

{of the' two before the oxyethylation step.

Also, if desired, the use of eth .lene-carbonate is a=very fact, it can be .oxyethylatedhwithout. theuse of, pressure.

One can oxyalkylate using an acid catalyst or an alkaline catalyst or at leastin part, without the use of any catalyst although such procedure is extremely slow and uneconomical. In other words, any one of the conventional catalysts used in oxyalkylation may be employed. It is our preference, however, to use an alkaline catalyst such as sodium methylate, caustic soda, or the like.

Actually, powdered pentaerythritol may contain 1% or somewhat less, of water. When such powder is heated to 140 to 150 and subjected to vacuum, particularly when anhydrous nitrogen is passed through the melted mass, the resultant product appears to become substantially water free. Even so, there may be a few tenths of a percent and perhaps only a trace of water remaining in some instances.

The products obtained by the above procedure usually show some color varying from a light amber to a pale straw.. They can be bleached in the usual fashion, using bleaching clays, charcoal, or anorganic bleach, such as alkaline catalyst which can be removed by conventional means, or they can be neutralizedby adding an equivalent amount of acid, such as hydrochloric acid. For many purposes the slight amount of residual alkalinity is not objectionable.

There are certain variants which can be employed without detracting from the metes and bounds of the invention, but for all practical purposes there is nothing to be gained by such variants and the result is merely increased cost. For instance, any one of the two oxides can be replaced to a minor percentage and usually to a very small degree, by oxide which would introduce substantially the same group along with a side chain, for

instance, one could employ glycidyl methyl ether, glycidyl or the like.

In the hereto appended claims reference has been Actually,

considered as hypothetically derived by reaction of be to Example 116 2, herein des'cribed.

pentaerythritol with the glycols, such as ethylene glycol,

butylene glycol, propylene glycol, or, polyglycols, For this reason there seems to be a preference to use the terminology glycol ethers of pentaerythritol.

Attention again is directed to What has been said previou'sly, to wit, that the fourreactantsas exemplified by the truncated triangular pyramid E, F, G, H, I, J, in the regular tetrahedron, A, B, C, D, as shown in Figure 1, might just as well be presented from any other position, that is, a position in which A, C, D, happen or B, C, D, or A,"B, D, happen to bethe base instead of A, B, C. However, such further elaboration would add nothing to what has been said previously and is' obviously omitted for purpose of brevity.

PART 4 As to the use of conventional demulsifying agent reference is made to US. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force in column 15 and ending in column 18, reference should Having thus described our invention,

what we claim as new and desire to'obtain by Letters Patent is:

4 free from isobutylene oxide.

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion" to a demulsifying agentin'cluding' a cogene'ric mixture 6f a-homologous series of glycol ethers of pentaerythritol;

said cogeneric mixture being derived exclusively from pentaerythritol, butylene oxide, propylene oxide and ethylene oxide in such weight proportions, so that the average composition of said cogeneric mixture stated in terms of the initial reactants, lies approximately within the truncated triangular pyramid identified as E, H, F, I, G and J in Figure 1, with the proviso that the percentage of ethylene oxide is within the limits of 2% to 39.5%, by weight, and the remaining three initial reactants recalculated to 100% basis, lie approximately Within the triangle defined in Figure 2 by points 1, 4 and 6.

2. The process of claim 1 with the proviso that oxyalkylation takes'place in presence of an alkaline catalyst.

3. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first.

4. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide is substantially 5. The process of claim 1 with the proviso that oxyalkylation takes place in presenceof an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide consists of or more of the 1,2-isomer and approximately 15% or less of the 2,3-isomeric form, and is substantially free from isobutylene oxide.

6. The processof claim 5 with the proviso that the reactantcomposition falls within the triangle defined by points 1, 2 and 8 in Figure 2.

7. The process of claim 5 with the proviso that the reactant composition falls within the triangle defined by points 2, 3 and 8 in Figure 2.

8. The process of claim 5 with the proviso that the reactant composition falls within the four-sided figure defined by points 8, 3, 9 and 7.

9. The process of claim 5 with the proviso that the reactant composition falls within the four-sided figure defined by points 3, 4, 5 and 9.

10. The process of claim S'With the proviso that the reactant composition falls within the triangle defined by points 5, 6 and 7.

11. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to a demulsifying agent including a cogeneric mixture 'of a homologous series of glycol ethers of pentaerythritol; said cogeneric mixture being derived exclus'ively' from rpent-aerythritol, butylene oxide, propylene oxide and ethylene oxide in such weightproportions, so that the average composition .of said cogeneric mixture stated in terms of. the initial reactants, lies approximately within the :truncated' triangular pyramid identified as E,

'H,F, I, G and] in Figure 1, with :the proviso that the percentage of ethylene oxide is within the limits of 2% to 39.5%, by weight, and'the remaining three initial reactants recalculated to" 100% basis, lie approximately within'the triangle defined in Figure 2 by points 1, 4 and 6; with the proviso that'thehydrophile properties of said cogeneric mixture in an equal Weight of Xylene, are sufficient to produce an emulsionwhen said xylene solution is shaken vigorously with one to three volumes of water. '12. The process of claimltl .viithihe proviso that oxyalkylation takes place in presenceLof an alkaline catalyst.

13. The'process ofclairn '11 With the proviso that oxyalkylation takes place in presence of an alkalinecatalyst and that the butylene oxide be added first.

14. The process of elaim' 1 1 .with the' proviso that oxyalkylation takes place in presenceof an alkaline catalyst and that the butyl e ne oxide be added first, and-Iwith the further proviso that the .butylene oxide is substantially free from isobutylene oxide.

15. The process of claim 11 with the proviso -that oxyalkylation takes; place in'presence of an alkaline: catalyst and that the butylene oxide be added =first,xandwwith 1.6 the further proviso that the butylene oxide consists of 185% or moreo'f the 1,2-isomer and approximately 15% 'or less 'fof'the 2,3 isomerioform, andis substantiallytree from isobutylene oxide.

' '16. The process of claim'li'with the;proviso'"that-the reactant'compositionfalls withinthe trian'gle' defined by 'pointsl; 2 and'8 in Figure 2.

17. The process'of claim 15 with'theproviso that the reactant composition falls Within the triangle defined by 18. The process of claim 15 'withtheproviso' that the reactant composition 'falls '.Wl-thl11'thIfOll1"Sld6d' figure defined by points 8, 3, 9 and .7.

19. 'The process of claim 'l5'with the proviso that'the reactant composition'falls 'withinwhe four-sided figure .de'fined' by points 3,4, 5 and 9.

- 'ZOI'The' proc'essof claim 15 with theaproviso that'the reactant composition falls withinpthe triangle defined by ,points 5, 6land 7.

References Cited in the file-of this patent UNITED STATES PATENTS 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO A DEMULSIFYING AGENT INCLUDING A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF PENTAERYTHRITOL, SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM PENTAERYTHRITOL, BUTYLENE OXIDE, PROPYLENE OXIDE AND ETHYLENE OXIDE IN SUCH WEIGHT PROPORTIONS, SO THAT THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURE STATED IN TERMS OF THE INITIAL REACTANTS, LIES APPROXIMATELY WITHIN THE TRUNCATED TRIANGULAR PYRAMID INDENTIFIED AS E,H,F,I, G AND I IN FIG 1, WITH THE PROVISO THAT THE THE PERCENTAGE OF ETHYLENE OXIDE IS WITHIN THE LIMITS OF 2% TO 39.5%, BY WEIGHT, AND THE REMAINING THREE INITIAL REACTANTS RECALCULATED TO 100% BASIS, LIE APPROXIMATELY WITHIN THE TRIANGLE DEFINED IN FIGURE 2 BY POINTS 1, 4 AND 6 